Sulfonated 2,2&#39;-bis (Diphenylphosphinomethyl)-1,1&#39;-binaphthalenes, process for their preparation and their use in a process for the hydroformylation of olefinically unsaturated compounds

ABSTRACT

Sulfonated diphosphines of the formula ##STR1## in which Ar is m--C 6  H 4  --SO 3  M, M is hydrogen, ammonium, a monovalent metal, or the chemical equivalent of a polyvalent metal; Ph is phenyl; the m&#39;s are individually 1 or 2, and the n&#39;s are individually 0, 1, or 2. A method of their preparation and the hydroformylation of olefins and olefinically unsaturated compounds using these compounds as a constituent of water-soluble catalyst systems are also disclosed.

PRIOR APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.240,901 filed May 11, 1994, now abandoned which is a division of U.S.patent application Ser. No. 066,553 filed May 25, 1993, now U.S. Pat.No. 5,347,045.

The invention relates to novel sulfonated diphosphines and to theirpreparation. They form complex compounds with metals of Group VIII ofthe Periodic Table of the Elements (IUPAC version) and can be used ascatalysts.

BACKGROUND OF THE INVENTION

Complex compounds containing a metal of Group VIII of the Periodic Tableas the central atom and, as ligands, P(III) compounds such as phosphinesor phosphites, and optionally other complexing groups, have recentlybecome increasingly important as catalysts. Thus the reaction,extensively practiced in industry, of olefins with carbon monoxide andhydrogen to yield aldehydes (hydroformylation) is carried out in thepresence of catalyst systems composed of rhodium and triphenylphosphine.Catalysts based on complex compounds containing phosphines have alsoproven successful for the reaction of methanol with synthesis gas togive higher alcohols, especially ethanol and propanol (homologization).In such cases, the ligands are usually present in excess, so that thecatalyst system is composed of complex compound and free ligand. Sincethese systems are soluble in organic media, the reaction is carried outin a homogeneous phase.

The reaction can also be carried out in the heterogeneous phase. Thisprocess variant is particularly convenient because it provides a simpleway of separating the water-dissolved catalyst from the water-insolublereaction product under mild conditions. The hydroformylation processdescribed in DE 26 27 354 C2, for example, works on this principle. Thesystem rhodium/sodium triphenylphosphine trisulfonate is used as thecatalyst.

In addition to monophosphines, diphosphines are also used asconstituents of catalyst systems in which the other component is a metalof Group VIII of the Periodic Table. For example, DE-A 40 40 315 relatesto the preparation of aldehydes by reaction of monoolefins,non-conjugated polyolefins, cycloolefins, or derivatives of theseclasses of compounds, with carbon monoxide and hydrogen in the presenceof rhodium/diphosphine catalysts. Sulfonated2,2'-bis(diphenylphosphinomethyl)biphenyls or2-(diphenylphosphinomethyl)-1-[2-diphenylphosphinomethyl)phenyl]naphthalenesare used as the diphosphines in this process. Together with the rhodium,they provide catalysts which are distinguished from the knownrhodium/monophosphine systems by increased activity.

SUMMARY OF THE INVENTION

The assumption that the composition of the product and the activity ofrhodium complex catalysts depend on the chemical characteristics of theligands creates an opportunity to develop novel ligands. This opens upthe possibility of varying the course of the reaction so that particularproducts are formed preferentially or--in some cases--even exclusively.It is further required that the ligands and the complex compounds formedtherefrom are soluble in water so as to benefit from the above-describedadvantages of hydroformylation in a two-phase system.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to novel sulfonated2,2'-bis(diphenylphosphinomethyl)-1,1'-binaphthalenes of the formula##STR2## wherein Ar is m--C₆ H₄ --SO₃ M, M is hydrogen, ammonium, amonovalent metal or the chemical equivalent of a polyvalent metal; Ph isphenyl; the m's individually are 1 or 2 and the n's are individually 0,1, or 2.

The parent substance used for the preparation of the novel compounds is2,2'-bis(diphenylphosphinomethyl)-1,1'-binaphthalene. This compound isobtained in a multistep synthesis by (1) reductive. dimerization of1-bromo-2-methylnaphthalene with magnesium to give2,2'-dimethyl-1,1'-binaphthalene, (2) reaction of the binaphthalene withbutyl lithium to give the dilithium compound, and (3) reaction of thedilithium compound with chlorodiphenylphosphine. Instead of reacting2,2'-dimethyl-1,1'-binaphthalene with butyl lithium, it is also possibleto convert it to 2,2'-bis(bromomethyl)-1,1'-binaphthalene withN-bromosuccinimide. Reaction of the dibromo compound with diphenylphosphinate gives2,2'-bis-(diphenylphosphinylmethyl)-1,1'-binaphthalene, which is reducedwith trichlorosilane to give2,2'-bis(diphosphinomethyl)-1,1'-binaphthalene. To introduce sulfonicacid groups into the binaphthyl radical and into the phenyl radicals,the diphosphine is treated with excess sulfur trioxide in the form ofoleum as the sulfonating agent.

Of importance for the degree of sulfonation which can be achieved arethe SO₃ concentration in the oleum, the reaction temperature, and thereaction time. These parameters are interrelated and influence eachother.

It has proven successful to use oleum containing at least 10% to 65% byweight of sulfur trioxide. The sulfonating agent is used in excess,based on the diphosphine. It is convenient to use 25 to 80, preferably40 to 70, mol of SO₃ per mol of2,2'-bis-(diphenylphosphinomethyl)-1,1'-binaphthalene. Oleum having ahigh concentration of free SO₃, i.e. a proportion of at least about 40%to 65% by weight, gives products which contain at least four SO₃ Hgroups and, therefore, have excellent water solubility. Concentrationsof free SO₃ in oleum which are lower than about 40% by weight giveproducts with a lesser degree of sulfonation, i.e. diphosphines whichhave only a limited water solubility.

The reaction temperature is 0° to 25° C., preferably 0° to 10° C. Inprinciple, it is also possible to use higher temperatures, but thesepromote the oxidation of the diphosphines to phosphine oxidesappreciably more than the sulfonation, so that the overall yield ofsulfonated phosphines decreases. Therefore, it is not recommended tocompensate for low concentrations of free SO₃ by raising the reactiontemperature. On the other hand, it is possible to influence the degreeof sulfonation of the diphosphine by means of the reaction time. Longerreaction times give compounds with a higher degree of sulfonation thanshorter reaction times. In general, the reaction requires 10 to 60 andpreferably 15 to 48 hours in the above temperature ranges. These timesapply especially when using oleum which contains about 40% by weight ormore of free oleum. Less concentrated oleum leads only to partiallysulfonated compounds, even with long reaction times; furthermore,increase in the formation of oxidation products cannot be fully avoided.It is therefore convenient to carry out the sulfonation with more highlyconcentrated oleum and to control the degree of sulfonation by means ofthe reaction time.

Concentrated sulfuric acid has proven successful as a solvent for thestarting compound to be sulfonated, namely,2,2'-bis(diphenylphosphinomethyl)-1,1'-binaphthalene. This solution canbe introduced into oleum in portions or oleum can be added theretoportionwise. It is recommended that the reaction mixture be stirredvigorously and thoroughly cooled; the reactants should be broughttogether slowly and in small portions so that the heat of reaction canbe dissipated without difficulty. By this means, rather than thesulfonation proceeding in an uncontrolled manner, SO₃ H groups areintroduced successively into the binaphthyl and phenyl radicals.Furthermore, oxidation of the phosphorus compound is effectivelyprevented. After all the sulfonating agent or diphosphine has beenadded, the after reaction can take place at room temperature, i.e. atabout 20° to 25° C., and essentially without external cooling. It isconvenient, however, to stir the reaction mixture at this stage as well,so that any heat of reaction still being produced is uniformlydistributed and can be dissipated without delay.

Following the sulfonation, the reaction solution is hydrolyzed. In thisprocess step, car should be taken to insure that the temperature doesnot exceed about 30° C.; moreover, it is advantageous to maintain thetemperature at 15° to 25° C. It is therefore recommended that thereaction mixture be carefully added to ice or hydrolyzed with ice orice-water with provision for intensive external cooling. The dilutesolution, containing essentially sulfuric acid and2,2'-bis(diphenylphosphinomethyl)-1,1'-binaphthalene with differentdegrees of sulfonation, is worked up in a further process step.

To do this, the solution containing sulfuric acid is neutralized with analkaline reagent such as an alkali metal hydroxide or alkali metalcarbonate, preferably sodium hydroxide. In order to maintain the volumeof the reaction mixture as low as possible and to precipitate asubstantial part of the alkali metal sulfate formed, the neutralizingagent is used as a highly concentrated solution or in undissolved solidform, e.g. flakes or pellets of caustic soda.

Because of its reduced solubility at lower temperatures, the bulk of thealkali metal sulfate can be removed from the solution by cooling. Theappropriate temperatures depend on the concentration of the sulfate inthe solution and the temperature profile of its solubility. The mostfavorable conditions therefore have to be determined by experiments ineach individual case. The sulfate can be separated off in one step or inseveral steps; it has proven convenient to carry out the crystallizationin two steps.

After separation of the alkali metal sulfate, the solution isconcentrated to dryness, preferably under an oil-pump vacuum, and thediphosphines with different degrees of sulfonation are extracted fromthe crystal slurry in the form of their alkali metal salts. Suitableextractants include mixtures of lower alcohols (i.e. alcohols having upto 5 carbon atoms in the molecule, such as methanol, ethanol orpropanol) with water. The extraction is carried out by conventionalmethods in one or more steps, preferably two to four steps. The extractsare combined and concentrated to dryness.

It has also proven successful to react the solution containing sulfuricacid with a mixture of a water-insoluble amine and an organic solventand to extract the sulfonates as amine salts. Suitable amines are thosehaving 10 to 60--preferably 13 to 36--carbon atoms, e.g.methyldioctylamine, tri-n-octylamine, triisooctylamine,tri-2-ethylhexylamine, and tridodecylamine, preferably triisooctylamine.Aliphatic and aromatic hydrocarbons or hydrocarbon mixtures, e.g.toluene or kerosene-like mixtures, especially toluene, are successfullyused as organic solvents.

0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, of amine is used per sulfonicacid equivalent. After vigorous mixing of the solution containingsulfuric acid and the amine solution, the aqueous and organic phases areseparated from one another. The organic phase, containing the aminesalt, is reacted with an aqueous solution of a base, the sulfonic acidsalt of-which is to be prepared. Examples of particularly suitable basesare sodium hydroxide and potassium hydroxide. This procedure gives anaqueous solution from which the desired sulfonic acid salt can beisolated.

Instead of the aqueous solution of the base being added all at once tothe solution of the amine salt in the organic medium, it can also beadded in portions. Such a gradual treatment of the amine solution, e.g.by adjusting the pH to certain values or ranges of values with the aidof the base, enables substantial separation of phosphine oxides from thesulfonation mixture and partial decomposition of the latter intoproducts with different degrees of sulfonation.

The novel sulfonated diphosphines are colorless solids. Depending on thesulfonation conditions, they contain up to six sulfonic acid groups. Thealkali metal salts are soluble in water and the solubility increaseswith the degree of sulfonation.

The free acids can be prepared by treating aqueous alkali metal saltsolutions of the sulfonated diphosphine with a cation exchanger of theH⁺ form. Other salts of the novel sulfonated diphosphines can beobtained from the acids by reaction with hydroxides, carbonates,ammonia, or amines.

The novel compounds have proven successful as components of catalystsystem containing metals of Group VIII of the Periodic Table. Incombination with rhodium, they are used especially as hydroformylationcatalysts. Accordingly, the invention further relates to a process forthe preparation of aldehydes by reaction of monoolefins, nonconjugatedpolyolefins, cycloolefins, or derivatives of these classes of compounds,with carbon monoxide and hydrogen at temperatures of 20° to 150° C. andpressures of 0.1 to 20 MPa in the presence of catalysts composed ofwater-soluble compounds of rhodium complexed with phosphines. Thewater-soluble phosphines used in the process are the above-describedsulfonated 2,2'-bis-(diphenylphosphinomethyl)-1,1'-binaphthyls.

The water-soluble rhodium/diphosphine complex compounds used ascatalysts in the novel process are distinguished by a remarkably highactivity, determined by the two criteria "activity" A and "productivity"P: ##EQU1##

The values of these two parameters achieved with the processes of thestate of the art are far exceeded by the procedure according to theinvention. The formation of normal aldehydes is greater and the amountsof noble metal and phosphine discharged with the reaction product aresmaller than in the known processes. Moreover, these results areobtained with a catalyst which has a distinctly smaller ligand/rhodiumratio than the catalysts used hitherto. These and other results of verygreat value for carrying out the process on the industrial scale couldnot be deduced from theoretical considerations nor predicted frompractical experience.

It is not necessary to use the sulfonated diphosphines as purecompounds. It is also possible to use diphosphines with differentdegrees of sulfonation and/or sulfonate mixtures with different cations.

It has proven successful not to use rhodium and the diphosphinesaccording to the invention in stoichiometric ratios, i.e. in accordancewith the chemical composition of the rhodium complex compound whichforms in the course of the hydroformylation reaction, but to use thediphosphines in excess. The ratio of rhodium to diphosphine can therebybe varied within wide limits and about 1 to 130 mol of diphosphine canbe used per mole of rhodium. The preferred molar ratio of rhodium todiphosphine is in the range from 1:2 to 1:25 and especially 1:2 to 1:10.

Rhodium is used as the metal or as a compound thereof. As the metal, itis finely divided or is precipitated in a thin layer on a support suchas activated charcoal, calcium carbonate, aluminum silicate, or clay.The rhodium compounds are substances which are water-soluble or whichbecome water-soluble under the reaction conditions. Suitable compoundsare the various rhodium oxides, rhodium salts of inorganic hydro acidsor oxy acids, and rhodium salts of aliphatic monocarboxylic orpolycarboxylic acids. Examples are rhodium nitrate, rhodium sulfate,rhodium acetate, rhodium 2-ethylhexanoate, and rhodium malonate. Rhodiumhalide compounds, on the other hand, are less useful because of thelower activity of the resulting complexes and the corrosive behavior ofthe halide ions. It is further possible to use rhodium carbonylcompounds such as Rh₃ (CO)₁₂ or Rh₆ (CO)₁₆, or complex salts of rhodium,e.g. cyclooctadienylrhodium compounds. Rhodium oxide and especiallyrhodium acetate and rhodium 2-ethylhexanoate are preferred. It can beassumed that water-soluble rhodium complex compounds containing carbonmonoxide and diphosphine as ligands are formed in the presence ofsynthesis gas under conditions of the hydroformylation reaction.Together with the excess diphosphine dissolved in the water, they makeup the catalyst system.

The catalyst solution is prepared from the components either in thehydroformylation reactor, or beforehand in a separate apparatus and thenintroduced into the hydroformylation reactor. The concentration ofrhodium in the aqueous catalyst solution is 10 to 500 ppm by weight(based on the solution), preferably 10 to 100 ppm by weight, andespecially 15 to 50 ppm by weight. The reaction temperature is betweenabout 20° and 150° C., preferably 80° to 140° C., and especially 100° to125° C.

The reaction of the olefin with carbon monoxide and hydrogen takes placeat pressures of about 0,1 to about 30 MPa, preferably 1 to 12 MPa, andespecially 1 to 5 MPa. The composition of the synthesis gas, i.e. thevolume ratio of carbon monoxide to hydrogen, can extend over a widerange and can be varied, for example, between 1:10 and 10:1. In general,gas mixtures are used in which the volume ratio of carbon monoxide tohydrogen is about 1:1 or only a slight variation from this value ineither direction.

The reaction of the reactants present in the liquid and gas phases takesplace in conventional reactors. The course of the reaction can beinfluenced by the fact that the aqueous catalyst solution must besaturated with the liquid or gaseous hydrophobic olefin and thesynthesis gas. It is therefore necessary to create the largest possiblecontact areas between the phases. A procedure which has provensuccessful is to vigorously stir the liquid reactor contents (catalystsolution, optionally liquid olefin, and reaction product) and introducethe gaseous reactants (synthesis gas and optionally olefin) into theliquid phase via distributing devices. A procedure which has proven verysuccessful is to keep the proportion of organic phase in the reactionmixture small. Surprisingly, the organic phase does not contribute tothe solubility of the reactants in the aqueous phase and the reactionproduct is prevented from undergoing undesirable secondary reactionswhich cannot be excluded when the residence time of the product in thereactor increases. Accordingly, the volume ratio of aqueous to organicphase is adjusted to from 1:1 to 100:1, preferably 10:1 to 100:1. Thiscan be done by continuously withdrawing an appropriate fraction of thereaction mixture from the reactor, separating the aqueous and organicphases from one another and recycling the aqueous phase into thereactor. The reaction can be carried out batchwise or, preferably,continuously.

The process according to the invention can be successfully applied tothe reaction of monoolefins, non-conjugated polyolefins, cyclic olefins,and derivatives of these unsaturated compounds. The olefins used are notsubject to any restrictions as far as molecular size is concerned. Theolefinically unsaturated compounds can be linear or branched, and thedouble bonds can be within or at the end of the chains. Examples ofolefins which can be used in the novel process are ethylene, propylene,butene-1, butene-2, pentene-1, 2-methylbutene-1, hexene-1, hexene-2,heptene-1, octene-1, octene-3, 3-ethylhexene-1, decene-1, undecene-3,4,4-dimethyl nonene-1, dicyclopentadiene, vinylcyclohexene,cyclooctadiene, and styrene. Derivatives of these olefins which can behydroformylated by the claimed procedure are e.g. alcohols, aldehydes,carboxylic acids, esters, nitriles, and halogen compounds, such as allylalcohol, acrolein, methacrolein, crotonaldehyde, methyl acrylate, ethylcrotonate, diethyl fumarate, diethyl maleate, and acrylonitrile. Theprocess is used with particular success for the hydroformylation ofolefins and olefin derivatives having 2 to 20 and especially 2 to 8carbon, atoms.

The following examples describe the preparation and properties of thenovel compounds (Examples 1 to 10) and their use as constituents ofcatalysts for the hydroformylation of olefinically unsaturated compounds(Examples 11 to 16).

EXAMPLE 1

10.11 g (15.54 mmol) of2,2'-bis(diphenylphosphinomethyl)-1,1'-binaphthalene is dissolved in 25ml of concentrated sulfuric acid at room temperature. The solution iscooled to 0° C. and 50 ml of 65% oleum are added dropwise, thetemperature being kept at a maximum of 10° C. The mixture issubsequently stirred for 48 hours Hydrolysis and neutralization arecarried out under conditions such that the temperature does not exceed25° C. The precipitated sodium sulfate is filtered off and the filtrateis stirred into methanol. The resulting white solid is separated off andthe filtrate is condentrated to dryness. The residue is taken up in justenough water for complete dissolution and the aqueous solution issprayed into twice the volume of methanol. The suspension obtained isfiltered and the filtrate is concentrated to dryness. The combinedfiltrates are analyzed.

Characterization:

Solubility: 1300 g/l of water

Elemental analysis: 13.8% by weight of sulfur; 4.42% by weight ofphosphorus; 9.9% by weight of sodium. The following molar ratios arecalculated therefrom: P:S=1:3; P:Na=1:3; S:Na=1:1, corresponding to theintroduction of six SO₃ H groups into the2,2'-bis(diphenylphosphinomethyl)-1,1'binaphthalene molecule ³¹ P NMR:S=-9.0

This compound is called below BINAS.

EXAMPLE 2

The sulfonation of 2,2-bis(diphenylphosphinomethyl)-1,1'-binaphthaleneis carried out according to Example 1 and the progress of the reactionis followed by NMR spectroscopy of the solution containing sulfuricacid. The following measured values are obtained:

³¹ P NMR: δ=-9.0 (hexasulfonated) δ=-9.89 (pentasulfonated) δ=-12.03(tetrasulfonated)

EXAMPLE 3-10

The sulfonation of 2,2-bis(diphenylphosphinomethyl)-1,1'-binaphthaleneis carried out according to Example 1, except that temperature, time,and SO₃ concentration are varied. The results are collated in the tablebelow. Examples 5, 6 and 7 are comparative, in which higher reactiontemperatures were used.

    ______________________________________                                               SO.sub.3 content                                                                          Reaction          Oxide                                           [% by weight]                                                                             time     Temperature                                                                            formation                                Example                                                                              of the oleum                                                                              [h]      [°C.]                                                                           [%].sup.a)                               ______________________________________                                        3      20          18       20        5                                       4      20          48       20       10                                       5      20          48       30       18                                       6      20          48       40       52                                       7      20          48       50       100                                      8      40          48       20        8                                       9      65          17       20        5                                       10     65          48       20       10                                       ______________________________________                                         .sup.a) previous standardization with completely oxidized, hexasulfonated     2,2bis(diphenylphosphinomethyl)-1,1binaphthalene                         

EXAMPLE 11

60.7 g (93.2 mmol) of 2,2-bis(diphenylphosphinomethyl)-1,1-binaphthaleneis dissolved in 300 g of concentrated sulfuric acid at 0° to 10° C.,601.7 g of 65% oleum is added with the temperature being kept at 0° to10° C. and the mixture is then stirred for 48 hours at room temperature.For hydrolysis, the sulfonation mixture is added dropwise to 3879.2 g ofwater over 30 min at temperatures below 10° C.

The sulfonation product is separated from the aqueous phase byextraction for 1 hour at 40° C. with a solution of 237.4 g oftriisooctylamine in 948.8 g of toluene. The organic phase (1307.8 g) isthen extracted at 40° C. with 3% by weight sodium hydroxide solution.

Up to a pH of 3.5, the aqueous phase (357.6 g) contains 16.8 mmol ofP(III) and 2.6 mmol of P(V), based in each case on one kilogram ofsolution, and 3.8% of sulfate. In the pH range 3.5 to 4.8, the P(III)content of the aqueous phase (463.0 g) is 163 mmol and the P(V) contentis 15.0 mmol, again based in each case on one kilogram of solution, andthe sulfate content is 0.05%. In the range from pH 4.8 to pH 6.0, theuseful product fraction (335.8 g) is separated off; it contains 212 mmolof P(III) and 1.0 mmol of P(V), based on one kilogram of solution.

EXAMPLE 12 to 17

Propylene and a CO/H₂ mixture made up of equal parts by volume areintroduced into a 0.2 liter stainless steel autoclave, equipped with astirrer, in an amount such that 10 liters/hour of off-gas can bewithdrawn from the reactor. 300 ml per hour of aqueous catalyst solution(261 mg of Rh as the acetate and 13.9 mmol of P(III) in the form ofBINAS, dissolved in 1000 ml of degassed water saturated with nitrogen)is simultaneously circulated through the reactor. The molar ratio ofphosphorus to rhodium is 5.5:1, corresponding to a ligand/rhodium ratioof 2.75:1. The reactants are reacted at a pressure of 5 MPa. Theremaining reaction parameters can be found in the Table.

In the Table, the results obtained with the process according to theinvention (Examples 12 to 16) are compared with the result obtained witha procedure according to the state of the art [catalyst: rhodium/sodiumtriphenylphosphinetrisulfonate (TPPTS)] (Example 17). The experimentsmake it clear that, in the novel process, with a surprisingly low Rh/Pratio, a high catalyst activity is achieved and the n/i ratio is furtherincreased. High conversions are obtained even when the olefin charge isconsiderably increased (Example 15).

While only a limited number of specific embodiments of the presentinvention have been expressly disclosed, it is, nonetheless, to bebroadly construed and not to be limited except by the character of theclaims appended hereto.

                                      TABLE                                       __________________________________________________________________________                                               Example 17                         Experimental conditions                                                                    Example 12                                                                          Example 13                                                                          Example 14                                                                          Example 15                                                                          Example 16                                                                          (Comparative)                      __________________________________________________________________________    Catalyst     Rh/BINAS                                                                            Rh/BINAS                                                                            Rh/BINAS                                                                            Rh/BINAS                                                                            Rh/BINAS                                                                            Rh/TPPTS                           Rhodium/ligand                                                                             1:2.75                                                                              1:2.75                                                                              1:2.75                                                                              1:2.75                                                                              1:2.75                                                                              1:100                              (mol/mol)                                                                     Temperature (°C.)                                                                   110   116   122   122   128   122                                Pressure (MPa)                                                                             5.0   5.0   5.0   5.0   5.0   5.0                                Propylene charge (g/h)                                                                     40.0  40.0  40.0  129.0 40.0  40.0                               Experimental results                                                          Conversion (%)                                                                             44.7  40.4  50.8  47.9  57.8  39.0                                ##STR3##    43.92 42.81 55.48 163.3 61.41 15.11                               ##STR4##    0.482 0.470 0.608 1.79  0.673 0.603                              n/i ratio    97/3  97/3  97/3  98/2  97/3  97/3                               (parts by weight)                                                             __________________________________________________________________________

What we claimed is:
 1. A water-soluble rhodium/diphosphine catalyst forhydroformylation of monoolefins, nonconjugated polyolefins,cycloolefins, and derivatives thereof, which catalyst is a complex ofrhodium and a sulfonated2,2'-bis(diphenylphosphinomethyl)-1,1'-binaphthalene of the formula##STR5## wherein Ar is m--C₆ H₄ --SO₃ M, M is hydrogen, ammonium, amonovalent metal, or a chemical equivalent of a polyvalent metal; Ph isphenyl, the m's are individually 1 or 2 and the n's are individually 0,1 or 2, said diphosphine having up to six sulfonic acid groups in amolar ratio of 1 mole of rhodium per 1 mole to 130 moles of diphosphine.2. The catalyst of claim 1 which contains 1 to 25 mol of saiddiphosphine per mol of rhodium.
 3. The catalyst of claim 2 whichcontains 1 to 10 mol of said diphosphine per mol of rhodium.